NREL/MP-425-20685
Development of an ASPEN PLUS
Physical Property Database for
Biofuels Components
Robert J. Wooley and
Victoria Putsche
National Renewable Energy Laboratory
1617 Cole Boulevard
Golden, Colorado 80401-3393
A national laboratory of the U.S. Department of Energy
Operated by Midwest Research Institute
For the U.S. Department of Energy
Under Contract No. DE-AC02-83CH10093
Prepared under Task Number BF521004
April 1996
1
Table of Contents
Page
Introduction ...................................................................................................................................................................1
Aspen’s Approach to Physical Properties................................................................................................................1
Minimum Physical Properties Required by Aspen ..................................................................................................1
Compounds Included ...................................................................................................................................................2
Combustion Stoichiometry ..........................................................................................................................................3
Description of Properties Included in the Database................................................................................................4
Glucose...........................................................................................................................................................5
Xylose.............................................................................................................................................................7
Cellulose.........................................................................................................................................................9
Xylan.............................................................................................................................................................10
Lignin ............................................................................................................................................................11
Cellulase (Enzyme)......................................................................................................................................11
Biomass (Cell Mass)...................................................................................................................................12
Zymo (Bacterium) ........................................................................................................................................12
Solslds (Soluble Solids)—Poplar Biomass..............................................................................................12
Solunkn (Unknown Soluble Solids)..........................................................................................................13
Gypsum.........................................................................................................................................................14
References ....................................................................................................................................................................15
Appendix A:
ASPEN PLUS DFMS (Data File Management System) Input File .......................................17
Appendix B:
ASPEN PLUS PROP-DATA Input File ....................................................................................23
Appendix C:
Quality of Properties in INHSPCD Databank for ASPEN PLUS...........................................28
Appendix D:
Values in ASPEN PLUS INHSPCD (NREL Biofuels) Databank............................................29
Appendix E:
Data Values in ASPEN PLUS NREL Biofuels INHSPCD Databank.....................................30
Appendix F:
ASPEN PLUS Physical Property Route Modifications to Enable the
DIPPR Liquid Heat Capacity Correlation.................................................................................32
2
Introduction
Physical property data for many of the key components used in the simulation for the ethanol from
lignocellulose process are not available in the standard ASPEN PLUS property databases. Indeed, many of
the properties necessary to successfully simulate this process are not available anywhere. In addition,
inputting the available properties into each simulation is awkward and tedious, and mistakes can be easily
introduced when a long list of physical property equation parameters is entered. Therefore, we must
evaluate the literature, estimate properties where necessary, and determine a set of consistent physical
properties for all of the components of interest. The components must then be entered into an in-house
NREL ASPEN PLUS database so they can be called upon without being retyped into each specific
simulation.
The first phase of this work has been completed. A complete set of properties for the currently identifiable
important compounds in the ethanol process is attached. With this as the starting base we can continue to
search for and evaluate new properties or have properties measured in the laboratory and update the central
database.
Aspen’s Approach to Physical Properties
The Aspen simulator handles three classes of compounds:
1.
Those (such as ethanol) that are involved in vapor liquid equilibrium;
2.
Those (such as CaSO4) that are solids only and are identifiable; and
3.
Solids (such as coal) that are identifiable by attribute only.
This database will deal with the first two types only.
For compounds involved in vapor liquid equilibrium, the simulator must have a complete set of properties to
allow it to do flash calculations. Even though the compound may be a very high boiler and will stay in the
liquid phase exclusively. Also, materials such as glucose and xylose, which are commonly solids, but will be
used exclusively in aqueous solution in the process, will be treated as liquids.
The second class, which includes cellulose and gypsum, is assumed to comprise conventional solids whose
property requirements are very minimal. A conventional solid can (unlike nonconventional solids that must
be described by attributes) be defined by a chemical formula.
Minimum Physical Properties Required by Aspen
The minimum physical properties required by Aspen depend on the calculation routes selected for
fundamental properties such as liquid, vapor and solid enthalpy and density. In general, because of the
need to distill ethanol and to handle dissolved gases the standard NRTL (non-random two liquid or Renon)
route is used. This route includes the NRTL liquid activity coefficient model, Henry’s law for the dissolved
gases, and RKS (Redlich-Kwong-Soave) equation of state for the vapor phase, is used to calculate
properties for components in the liquid and vapor phases. It also uses the Ideal Gas (IG) at 25° C as the
standard reference state, thus requiring the heat of formation at these conditions (Table 1).
3
Table 1.
Required Properties
Liquids/Gases
Conventional Solids
Critical Temperature
Heat of Formation
Critical Pressure
Heat Capacity
I.G. Heat of Formation
Density
Vapor Pressure
I. G. Heat Capacity
Heat of Vaporization
Liquid Density
Many components used here will not be involved in vapor liquid equilibrium, as they stay in the liquid
phase under the operating conditions experienced during the ethanol process. However, because of the
above requirements, vapor properties will be needed. These will be estimated, but as long as the vapor
pressure is low enough, the compounds will never actually show up in the vapor phase, and the liquid
properties of interest will be calculated correctly.
Compounds Included
Table 2 lists the compounds included in the current database, along with their primary state and formula.
Isomers were not considered independently; because most of the desired properties are being estimated,
there will not be a significant difference between isomers. This will not preclude the use of isomers in
simulations, but there will be no physical difference between isomers in the simulations. For example, all
five-carbon sugars should use the properties of xylose, and six-carbon sugars those of glucose. The
chemical formulas used for compounds such as biomass and cellulase were obtained from Radian
Corporation1 and Putsche, 2 respectively. Solslds are essentially everything combustible that is not one of
the identifiable cellulose, lignin, or hemicellulose materials in biomass. The formula for solslds corresponds
to the difference between the ultimate analysis of the biomass and the number of identifiable compounds.
The heating value of solslds is the difference between that of the original biomass and the sum of the
identifiable components. The solslds listed here correspond to poplar biomass and would differ for other
sources of biomass. The solunkn is a compound that elutes at a similar position to xylitol, but is unknown.
It was given a reduced formula of xylose for material balances only.
4
Table 2.
Compounds Included in the ASPEN+ In House Database (INHSPCD)
Compound Name
Formula
Database Name
Database Alias
Normal State
Glucose
C6H12O6
GLUCOSE
C6H12O6
Liquid
Xylose
C5H10O5
XYLOSE
C5H10O5
Liquid
Cellulose
C6H10O5
CELLULOS
C6H10O5
Solid
Xylan
C5H8O4
XYLAN
C5H8O4
Lignin
C7.3H13.9O1.3
LIGNIN
CXHXOX
Solid
Biomass (cell mass)
CH1.64N0.23O0.39S0.0035
BIOMASS
CHXNXOXSX-1
Solid
Cellulase
CH1.57N0.29O0.31S0.007
CELLULAS
CHXNXOXSX-2
Solid
Zymo
CH1.8O0.5N0.2
ZYMO
CHXOXNX
Solid
Solslds
CH1.48O0.19S0.0013
SOLSLDS
CHXOXSX
Liquid
Solunkn
C0.5HO0.5
SOLUNKN
CXHOX
Liquid
Gypsum
CaSO4⋅2H2O
GYPSUM
CaSO4-2H2O
*For the polymeric compounds a formula corresponding to a single repeat unit was used.
Solid
Solid
Combustion Stoichiometry
In all cases the heat of combustion was found in the literature or estimated and used to calculate the heat of
formation. To calculate the heat of formation necessary for other heat of reaction calculations, we must
know the compound’s molecular formula (and consequently its combustion stoichiometry). Given the
above molecular formulas, the combustion stoichiometry used for each compound is given below.
Glucose
C6H12O6 + 6 O2 → 6 H2O + 6 CO2
Xylose
C5H10O5 + 5 O2 → 5 H2O + 5 CO2
Cellulose
C6H10O5 + 6 O2 → 5 H2O + 6 CO2
Xylan
C5H8O4 + 5 O2 → 4 H2O + 5 CO2
Lignin
C7.3H13.9O1.3 + 10.125 O2 → 6.95 H2O + 7.3 CO2
5
Biomass
CH1.64N0.23O0.39S0.0035 + 1.2185 O2 → 0.82 H2O + CO2 + 0.0035 SO2 + 0.115 N2
Cellulase
CH1.57N0.29O0.31S0.007 + 1.2445 O2 → 0.785 H2O + CO2 + 0.007 SO2 + 0.145 N2
Zymo
CH1.8O0.5N0.2 + 1.2 O2 → 0.9 H2O + CO2+ 0.1 N2
Solslds
CH1.48O0.19S0.0013 + 1.2763 O2 → 0.74 H2O + CO2+ 0.0013 SO2
Solunkn
C0.5HO0.5 + 0.5 O2 → 0.5 H2O + 0.5 CO2
In addition to the reaction stoichiometry, the heat of formation of the combustion products is required to
calculate heat of formation from heat of combustion. The values used here are:
Compound
H2O (liquid)
CO2 (IG)
SO2 (IG)
Heat of Formation @298 K
-68.7979 kcal/mole
-2.88043x108 J/Kmole
-94.052 kcal/mole
-3.93776x108 J/Kmole
-70.899 kcal/mole
-2.9684x108 J/Kmole
These values were taken from the ASPEN PLUS Pure Component databank to be consistent with the
calculations to be performed in ASPEN PLUS.
Description of Properties Included in the Database
Following is a description of the source methods and estimations used to develop properties for all
compounds listed above. These properties are in the new ASPEN PLUS INHSPCD (In-house Pure
Component Database) and are enclosed as inputs to DFMS (Data File Management System) (Appendix A)
and as ASPEN PLUS Input language PROP-DATA statements (Appendix B). (All properties are in SI units.)
A summary of sources of all properties appears in Appendix C and a summary of the properties in the inhouse database appears in Appendix D.
The ASPEN PLUS DFMS allows a source code to be entered for each property. Rather than using an actual
reference number, this is used for a quality code. The following quality codes have been assigned to each
data set. In general, data with a higher confidence level correspond to higher numbers.
Code
9
8
7
6
5
4
3
2
1
0
Data Quality Codes Used in the Biofuels INHSPCD
Code Description
Literature data
Regressed to literature data
Calculated directly (e.g. MW)
o
Calculated from other literature data (e.g. ∆H F from ∆H COMB )
Estimated from the commercial property estimation package PREDICT
Estimated, but not from PREDICT
Copied literature data from a similar compound on a mass basis
Copied literature data from a similar compound on a mole basis
Copied data of various origin from a similar compound
Unknown origin
7
Glucose
Glucose, although generally considered a solid at the temperatures involved in the ethanol process, is
exclusively in aqueous solution. It will therefore be modeled as a liquid, although it will never exist as a pure
liquid in the process. The properties listed here are NOT intended for use with pure glucose, or even with
concentrated solutions. The vapor pressure is low enough (the normal boiling point has been estimated to
be higher than 800 K) that the glucose will never be flashed into the vapor stream.
Point Properties
Properties
(Quality Code)
Molecular Weight
Critical Temperature
(7)
(5)
Critical Pressure
(5)
Critical Volume
(5)
Acentric Factor
(5)
I.G. Heat of Formation
(6)
Methodology
Calculated directly.
Estimated using the Joback1 group contribution method in
PREDICT.
Estimated using the Joback1 group contribution method in
PREDICT.
Estimated using the Joback1 group contribution method in
PREDICT.
Estimated using the Pitzer2 vapor pressure correlation and the
estimated normal boiling point in PREDICT.
Literature 5 value was -1.2735x109 J/Kmole. Using this value, and
the ∆HF(liq) calculated from the literature value for higher ∆HC
(673 kcal/mole 4) the heat of vaporization (difference between
∆HF(I.G.) and ∆HF (liquid or solid, ∆HSOLN is small)) would have to
be less than zero. Therefore, the heat of vaporization was set at a
very small value (see below) and the ∆HF(I.G.) from the literature
was adjusted slightly to give the value of -1.2569x109 J/Kmole
used in the database. See Table 3 for a comparison of the
original ∆HC and those back calculated from Aspen.
I.G. Free Ergy of Form. (9) Literature 5
@ 298.15 K
Table 3.
High Heating Values (Heat of Combustion) Comparison of ASPEN Calculated Values
and Literature
Higher Heating Values Calculated from ASPEN
J/Kmol
Kcal/gmole BTU/lbmole BTU/lb
180.16 2.81776E+09
673.01
1212242 6728.70
150.132 2.35178E+09
561.71
1011771 6739.21
162.1436 2.81312E+09
671.90
1210246 7464.04
132.117 2.34787E+09
560.78
1010089 7645.41
122.493 3.26548E+09
779.95
1404858 11468.88
MW
Glucose
Xylose
Cellulose
Xylan
Lignin
Biomass
Zymo
Cellulase
Solslds
Solunkn
EtOH
Glucose
Xylose
23.238
24.6264
22.8398
16.5844
15.0134
5.31676E+08
5.20125E+08
5.44906E+08
5.53575E+08
2.16411E+08
126.99
124.23
130.15
132.22
51.69
228734.9 9843.14
223765.5 9086.41
234426.7 10263.95
238156.2 14360.25
93103.23 6201.34
46.0691 1.36661E+09
326.41
587935.9 12762.04
Heat of Reaction to Form Ethanol Calc from ASPEN
180.16 8.45388E+07
150.132 7.41032E+07
20.19
17.70
36369.85
31880.3
8
201.88
212.35
Higher Heating Values Calc. from Literature
J/Kmol
Kcal/gmole BTU/lbmole BTU/lb
673
561.5
2.81311E+09 671.8987
1210240 7464
560.6
3.26751E+09 780.4304
1405730 11476
5.32425E+08
5.45015E+08
127.1674
124.8
130.1745
132.7
52
229057
9857
234473.4 10266
327.6
Heat of Rxn to Form Ethanol from Literature
19.6
15.5
Temperature Correlated Properties
Properties
(Quality Code)
Vapor Pressure
(5)
I.G. Heat Capacity
(6)
Heat of Vaporization
(0)
Liquid Density
(8)
Liquid Heat Capacity
(9)
Methodology
Estimated using the Pitzer4 corresponding states method with
the above critical properties and fit to the ASPEN PLUS PLXANT
extended Antoine model.
Used a constant value for solid glucose at 20°C from the
literature 6 and assumed it was the same as the liquid heat
capacity. Using the heat of vaporization listed below, a single
parameter in this equation was adjusted to match the liquid heat
capacity.
Set to an arbitrarily low value of 0.12 kcal/mole (5.02x105 J/Kmole)
at 298 K. The standard exponent for the Watson7 equation of
0.38 was used with the set value at 298 K in the Aspen DHVLWT
(Watson) correlation.
The Aspen single parameter in the Rackett8 was regressed using
literature 6 data for glucose water solutions and water data from
the Aspen PURECOMP database. The results of this regression
are given in Table 1.
Used a constant value for solid glucose at 20o C from the
literature 6.
9
Table 4.
Density
Mole Frac Data
H2O
g/cc
Glucose/Water Solution Density at 20 C, Regression to the ASPEN Plus Rackett Equation
Density
Density
Density
Estimated
g/cc
Std-Dev
Absolute
Diff.
0.9995
1.0001 1.00023 1.00E-02 1.32E-04
0.99899
1.002 1.00215 1.00E-02 1.52E-04
0.99848
1.0039 1.00408 1.00E-02 1.78E-04
0.99796
1.0058 1.00602 1.01E-02 2.18E-04
0.99744
1.0078 1.00796 1.01E-02 1.59E-04
0.99692
1.0097 1.00991 1.01E-02 2.13E-04
0.99639
1.0116 1.01188 1.01E-02 2.76E-04
0.99585
1.0136 1.01384 1.01E-02 2.44E-04
0.99531
1.0155 1.01582 1.02E-02 3.24E-04
0.99477
1.0175 1.01781 1.02E-02 3.08E-04
0.99421
1.0194
1.0198 1.02E-02 4.04E-04
0.99366
1.0214 1.02181 1.02E-02 4.07E-04
0.9931
1.0234 1.02382 1.02E-02 4.21E-04
0.99253
1.0254 1.02584 1.03E-02 4.39E-04
0.99196
1.0274 1.02787 1.03E-02 4.71E-04
0.99138
1.0294 1.02991 1.03E-02 5.05E-04
0.9908
1.0314 1.03195 1.03E-02 5.53E-04
0.99021
1.0334 1.03401 1.03E-02 6.07E-04
0.98961
1.0354 1.03607 1.04E-02 6.70E-04
0.98901
1.0375 1.03814 1.04E-02 6.42E-04
0.98779
1.0416 1.04231 1.04E-02 7.08E-04
0.98655
1.0457 1.04651 1.05E-02 8.12E-04
0.98528
1.0498 1.05074 1.05E-02 9.44E-04
0.98398
1.054 1.05501 1.05E-02 1.01E-03
0.98266
1.0582 1.05932 1.06E-02 1.12E-03
ROOT MEAN SQUARE DEVIATION = 0.2490574E-02
AVERAGE DEVIATION = 0.7325108E-03
AVERAGE ABSOLUTE DEVIATION = 0.1670345E-02
MAXIMUM DEVIATION =-0.1024660E-01
RMS RELATIVE DEVIATION = 0.2061817E-02
AVG. ABS. REL. DEVIATION = 0.1445592E-02
Percent
Diff.
1.32E-02
1.52E-02
1.78E-02
2.17E-02
1.58E-02
2.11E-02
2.73E-02
2.41E-02
3.19E-02
3.03E-02
3.96E-02
3.99E-02
4.12E-02
4.28E-02
4.58E-02
4.91E-02
5.37E-02
5.88E-02
6.47E-02
6.19E-02
6.79E-02
7.76E-02
9.00E-02
9.61E-02
0.10542
Mole Frac Data
H2O
g/cc
0.98131
0.97993
0.97852
0.97708
0.97561
0.97257
0.96939
0.96606
0.96257
0.95891
0.95506
0.95101
0.94675
0.94225
0.9375
0.93248
0.92715
0.9215
0.9155
0.90909
0.90226
0.89495
0.8871
0.87866
0.86957
1.0624
1.0667
1.071
1.0753
1.0797
1.0884
1.0973
1.1063
1.1154
1.1246
1.134
1.1434
1.1529
1.1626
1.1724
1.1823
1.1924
1.2026
1.213
1.2235
1.2342
1.2451
1.2562
1.2676
1.2793
Estimated
g/cc
Std-Dev
1.06365
1.06801
1.07241
1.07684
1.08131
1.09033
1.09946
1.10871
1.11807
1.12753
1.13708
1.1467
1.1564
1.16614
1.17592
1.18571
1.19549
1.20523
1.2149
1.22447
1.2339
1.24313
1.25211
1.26077
1.26905
1.06E-02
1.07E-02
1.07E-02
1.08E-02
1.08E-02
1.09E-02
1.10E-02
1.11E-02
1.12E-02
1.12E-02
1.13E-02
1.14E-02
1.15E-02
1.16E-02
1.17E-02
1.18E-02
1.19E-02
1.20E-02
1.21E-02
1.22E-02
1.23E-02
1.25E-02
1.26E-02
1.27E-02
1.28E-02
Absolute
Diff.
1.25E-03 0.11747
1.31E-03 0.12319
1.41E-03 0.13199
1.54E-03 0.14352
1.61E-03
0.149
1.93E-03 0.17694
2.16E-03
0.1969
2.41E-03 0.21817
2.67E-03 0.23943
2.93E-03 0.26046
3.08E-03 0.27137
3.30E-03 0.28886
3.50E-03
0.3032
3.54E-03 0.30437
3.52E-03 0.29985
3.41E-03 0.28804
3.09E-03 0.25884
2.63E-03 0.21854
1.90E-03 0.15688
9.73E-04 7.95E-02
-3.04E-04 -2.46E-02
-1.98E-03 -0.15863
-4.09E-03 -0.32591
-6.83E-03 -0.53851
-1.02E-02 -0.80095
Xylose
Xylose, like glucose, is generally considered a solid at the temperatures involved in the ethanol process, but
is exclusively in aqueous solution. Therefore, it will be modeled as a liquid, although it will never exist as a
pure liquid in the process. The properties listed here are NOT intended for use with pure xylose or even
with concentrated solutions. The vapor pressure is sufficiently low enough (the normal boiling point has
been estimated to be higher than 800 K) that the xylose will never be flashed into the vapor stream.
10
Percent
Diff.
Point Properties
Properties
(Quality Code)
Molecular Weight
Critical Temperature
(7)
(5)
Critical Pressure
(5)
Critical Volume
(5)
Acentric Factor
(5)
I.G. Heat of Formation
@ 298.15 K
(6)
Methodology
Calculated directly.
Estimated using the Joback3 group contribution method in
PREDICT.
Estimated using the Joback3 group contribution method in
PREDICT.
Estimated using the Joback3 group contribution method in
PREDICT.
Estimated using the Pitzer4 vapor pressure correlation and the
estimated normal boiling point in PREDICT.
As with glucose, the heat of vaporization was set at an arbitrarily
low value and the ∆HF(I.G.) was back calculated using that heat
of vaporization and the literature value of heat of combustion
(561.5 Kcal/mole 6) See Table 3 for a comparison of the original
∆HC and that back calculated from Aspen.
Temperature Correlated Properties
Properties
(Quality Code)
Vapor Pressure
(5)
I.G. Heat Capacity
(3)
Heat of Vaporization
(0)
Liquid Density
(3)
Liquid Heat Capacity
(3)
Methodology
Estimated using the Pitzer4 corresponding states method with the
above critical properties and fit to the ASPEN PLUS PLXANT
extended Antoine model.
Used a constant value for solid glucose at 20°C from the
literature 6 and assumed it was the same as the liquid heat
capacity. Using the heat of vaporization listed below, a single
parameter in this equation was adjusted to match the liquid heat
capacity.
Set to an arbitrarily low value of 1 Kcal/mole (4.1868x106) at 298 K.
The standard exponent for the Watson7 equation of 0.38 was
used with the set value at 298 K in the Aspen DHVLWT
(Watson) correlation.
The Aspen single parameter in the Rackett8 was regressed using
the literature 6 data for glucose water solutions on a mass basis
(g/L) and water data from the Aspen PURECOMP database. The
results of this regression are given in Table 5.
Used a constant value for solid glucose at 20o C from the
literature 6.
11
Table 5. Xylose/Water Solution Density at 20 C, Regression to the ASPEN Plus Rackett Equation
Using Glucose/Water data on a mass basis, converted to Xylose/Water on a mole basis
Density
Density
Density
Density
Mole Frac Data
Estimated
Absolute Percent
Mole Frac Data
Estimated
H2O
g/cc
g/cc
Std-Dev
Diff.
Diff.
H2O
g/cc
g/cc
Std-Dev
0.9995
1.0001 1.00001 1.00E-02 -8.63E-05
0.99899
1.002 1.00172 1.00E-02 -2.84E-04
0.99848
1.0039 1.00343 1.00E-02 -4.74E-04
0.99796
1.0058 1.00515 1.01E-02 -6.50E-04
0.99744
1.0078 1.00688 1.01E-02 -9.22E-04
0.99692
1.0097 1.00862 1.01E-02 -1.08E-03
0.99639
1.0116 1.01037 1.01E-02 -1.23E-03
0.99585
1.0136 1.01213 1.01E-02 -1.47E-03
0.99531
1.0155
1.0139 1.02E-02 -1.60E-03
0.99477
1.0175 1.01568 1.02E-02 -1.82E-03
0.99421
1.0194 1.01747 1.02E-02 -1.93E-03
0.99366
1.0214 1.01927 1.02E-02 -2.13E-03
0.9931
1.0234 1.02108 1.02E-02 -2.32E-03
0.99253
1.0254
1.0229 1.03E-02 -2.50E-03
0.99196
1.0274 1.02473 1.03E-02 -2.67E-03
0.99138
1.0294 1.02657 1.03E-02 -2.83E-03
0.9908
1.0314 1.02843 1.03E-02 -2.97E-03
0.99021
1.0334 1.03029 1.03E-02 -3.11E-03
0.98961
1.0354 1.03216 1.04E-02 -3.24E-03
0.98901
1.0375 1.03405 1.04E-02 -3.45E-03
0.98779
1.0416 1.03785 1.04E-02 -3.76E-03
0.98655
1.0457 1.04169 1.05E-02 -4.01E-03
0.98528
1.0498 1.04558 1.05E-02 -4.22E-03
0.98398
1.054 1.04951 1.05E-02 -4.49E-03
0.98266
1.0582
1.0535 1.06E-02 -4.71E-03
ROOT MEAN SQUARE DEVIATION = 0.3947574E-02
AVERAGE DEVIATION =-0.2042724E-02
AVERAGE ABSOLUTE DEVIATION = 0.3407739E-02
MAXIMUM DEVIATION = 0.8294807E-02
RMS RELATIVE DEVIATION = 0.3518716E-02
AVG. ABS. REL. DEVIATION = 0.3078164E-02
-8.63E-03
-2.83E-02
-4.72E-02
-6.46E-02
-9.15E-02
-0.10706
-0.12154
-0.14515
-0.15755
-0.17908
-0.18948
-0.20869
-0.22661
-0.24389
-0.25962
-0.27476
-0.28839
-0.30117
-0.3128
-0.33292
-0.36054
-0.38333
-0.4021
-0.42565
-0.44467
0.98131
0.97993
0.97852
0.97708
0.97561
0.97257
0.96939
0.96606
0.96257
0.95891
0.95506
0.95101
0.94675
0.94225
0.9375
0.93248
0.92715
0.9215
0.9155
0.90909
0.90226
0.89495
0.8871
0.87866
0.86957
1.0624
1.0667
1.071
1.0753
1.0797
1.0884
1.0973
1.1063
1.1154
1.1246
1.134
1.1434
1.1529
1.1626
1.1724
1.1823
1.1924
1.2026
1.213
1.2235
1.2342
1.2451
1.2562
1.2676
1.2793
1.05752
1.06159
1.06571
1.06988
1.0741
1.08269
1.09147
1.10047
1.10968
1.1191
1.12875
1.13862
1.14872
1.15905
1.16961
1.18041
1.19144
1.20271
1.21421
1.22593
1.23787
1.25003
1.26238
1.27491
1.2876
1.06E-02
1.07E-02
1.07E-02
1.08E-02
1.08E-02
1.09E-02
1.10E-02
1.11E-02
1.12E-02
1.12E-02
1.13E-02
1.14E-02
1.15E-02
1.16E-02
1.17E-02
1.18E-02
1.19E-02
1.20E-02
1.21E-02
1.22E-02
1.23E-02
1.25E-02
1.26E-02
1.27E-02
1.28E-02
Absolute
Diff.
-4.88E-03 -0.45941
-5.11E-03 -0.47887
-5.29E-03 -0.49362
-5.42E-03 -0.50394
-5.60E-03 -0.51848
-5.71E-03 -0.52493
-5.83E-03 -0.53108
-5.83E-03 -0.52699
-5.72E-03 -0.51315
-5.50E-03 -0.48891
-5.25E-03 -0.46317
-4.78E-03 -0.41832
-4.18E-03 -0.36294
-3.55E-03 -0.30577
-2.79E-03 -0.23814
-1.89E-03 -0.16019
-9.60E-04 -8.05E-02
1.06E-04 8.81E-03
1.20E-03 9.93E-02
2.43E-03 0.19859
3.67E-03 0.29769
4.93E-03 0.39573
6.18E-03 0.49187
7.31E-03 0.57665
8.29E-03 0.64839
Cellulose
Cellulose is considered to be a solid throughout the process and will never be in solution. Additionally,
cellulose is a polymer, but its molecular weight formula will be taken as the repeat unit only. The other
properties are determined on a weight basis and then converted to mole basis for the database, using the
molecular weight of a repeat unit.
Point Properties
Properties
(Quality Code)
Molecular Weight
Solid Heat of Formation
@ 298.15 K
(7)
(6)
Methodology
Calculated directly.
Using the a literature value for ∆Hc 10 the heat of formation
was back calculated. See Table 3 for the original values of ∆Hc .
12
Percent
Diff.
Temperature Correlated Properties
Properties
(Quality Code)
Solid Heat Capacity
(9)
Solid Density
(3)
Methodology
A literature polynomial10 for cellulose from loblolly pine wood on
a mass basis was used.
A literature value for starch11 was used on a mass basis.
Xylan
Xylan is considered to be a solid throughout the process and will never be in solution. Additionally, xylan
is a polymer, but its molecular weight formula will be taken as the repeat unit only. The other properties are
determined on a weight basis and then converted to mole basis for the database, using the molecular weight
of a repeat unit.
Point Properties
Properties
(Quality Code)
Molecular Weight
Solid Heat of Formation
@ 298.15 K
(7)
(2)
Methodology
Calculated directly.
Assumed that the ratio of the ∆Hc of glucose to xylose
would be the same as that for the ratio of cellulose to xylan.
Using the glucose to xylose ∆Hc ratio and the ∆Hc from above for
cellulose, the ∆Hc for xylan was approximated. From the ∆Hc , the
heat of formation was calculated.
Temperature Correlated Properties
Properties
(Quality Code)
Solid Heat Capacity
(3)
Solid Density
(3)
Methodology
A literature polynomial10 for cellulose from loblolly pine wood on
a mass basis was used.
A literature value for starch11 was used on a mass basis.
Lignin
Lignin is considered to be a solid throughout the process and will never be in solution.
Point Properties
Properties
(Quality Code)
Molecular Weight
Solid Heat of Formation
@ 298.15 K
(7)
(6)
Methodology
Calculated directly.
Used ∆Hc value supplied by Riley15 to calculate the heat of
formation. The ∆Hc of Riley value is similar to a value given by
the literature for softwood. Softwood literature 14 value, 11340
BTU/#, Riley’s value 11476 BTU/#.
13
Temperature Correlated Properties
Properties
(Quality Code)
Solid Heat Capacity
Solid Density
(9)
(3)
Methodology
Used literature value for polynomial14.
Simply assume 1.5 g/cc (similar to starch).
Cellulase (Enzyme)
Cellulase is considered to be a solid throughout the process and will never be in solution.
Point Properties
Properties
(Quality Code)
Molecular Weight
Solid Heat of Formation
@ 298.15 K
(7)
(6)
Methodology
Calculated directly.
Used ∆Hc value supplied by Putsche2 to calculate the heat of
formation. Putsche calculated the ∆Hc using the approximation
method of Bailey and Ollis 13.
Temperature Correlated Properties
Properties
(Quality Code)
Solid Heat Capacity
Solid Density
(4)
(3)
Methodology
Estimated using Kopp’s rule 6.
Simply assume 1.5 g/cc (similar to starch).
Biomass (Cell Mass)
Biomass is considered to be a solid throughout the process and will never be in solution.
Point Properties
Properties
(Quality Code)
Molecular Weight
Solid Heat of Formation
@ 298.15 K
(7)
(6)
Methodology
Calculated directly.
Used ∆Hc value supplied by Putsche2 to calculate heat of
formation. Putsche calculated the ∆Hc using the approximation
method of Bailey and Ollis 13.
Temperature Correlated Properties
Properties
(Quality Code)
Solid Heat Capacity
Solid Density
(4)
(3)
Methodology
Estimated using Kopp’s rule 6.
Simply assume 1.5 g/cc (similar to starch).
Zymo (Bacterium)
Zymo is considered to be a solid throughout the process and will never be in solution.
14
Point Properties
Properties
(Quality Code)
Molecular Weight
Solid Heat of Formation
@ 298.15 K
(7)
(4)
Methodology
Calculated directly.
Estimated ∆Hc using a crude method of Bailey and Ollis 16
and then calculated the heat of formation.
Temperature Correlated Properties
Properties
Solid Heat Capacity
Solid Density
(Quality Code)
(4)
(3)
Methodology
Estimated using Kopp’s rule 6.
Simply assume 1.5 g/cc (similar to starch).
Solslds (Soluble Solids)—Poplar Biomass
Solslds are the nonidentifiable solids that will be dissolved in aqueous solutions throughout the simulation.
Therefore, they will never exist as a pure liquid in the process. The properties listed here are NOT intended
for use with pure components or even with concentrated solutions. The vapor pressure is low enough (the
normal boiling point has been estimated to be higher than 800 K) such that the solslds will never be flashed
into the vapor stream.
Point Properties
Properties
Molecular Weight
Critical Temperature
Critical Pressure
Critical Volume
Acentric Factor
I.G. Heat of Formation
@298.15 K
(Quality Code)
(7)
(1)
(1)
(1)
(1)
(4)
Methodology
Calculated directly.
Used the value of glucose.
Used the value of glucose.
Used the value of glucose.
Used the value of glucose.
∆Hc value calculated to match the ∆Hc of poplar biomass and its
identifiable components. This was verified using a crude
method of Bailey and Ollis 13. This value was then used to
calculated the heat of formation of the liquid. A small value of 1
kcal/mole was assumed for the heat of vaporization and the I.G.
heat of formation was calculated.
Temperature Correlated Properties
Properties
(Quality Code)
Vapor Pressure
I.G. Heat Capacity
(1)
(1)
Heat of Vaporization
(0)
Methodology
Used the value of glucose.
Used a constant value for solid glucose at 20°C from the
literature 6 and assumed it was the same as the liquid heat
capacity. Using the heat of vaporization listed below, a single
parameter in this equation was adjusted to match the liquid heat
capacity.
Assumed an arbitrary low value of 1 kcal/mole at 298 K.
15
Liquid Density
(0)
Liquid Heat Capacity
(3)
Assuming a value of water (1 g/cc) the Rackett parameter was
back calculated using the above critical properties and molecular
weight.
Used value for glucose on a mass basis.
Solunkn (Unknown Soluble Solids)
Solunkn is an unknown compound similar to xylose that will be dissolved in aqueous solutions throughout
the simulation. Therefore, it will never exist as a pure liquid in the process. The properties listed here are
NOT intended for use with pure compounds or even with concentrated solutions. The vapor pressure is
sufficiently low (the normal boiling point has been estimated to be higher than 800 K) such that the solunkn
will never be flashed into the vapor stream.
Point Properties
Properties
(Quality Code)
Molecular Weight
Critical Temperature
Critical Pressure
Critical Volume
Acentric Factor
I.G. Heat of Formation
@ 298.15 K
(7)
(1)
(1)
(1)
(1)
(4)
Methodology
Calculated directly.
Used the value of glucose.
Used the value of glucose.
Used the value of glucose.
Used the value of glucose.
Estimated ∆Hc using a crude method of Bailey and Ollis 13
and then calculated the heat of formation of the liquid. A small
value of 1 kcal/mole was assumed for the heat of vaporization
and the I.G. heat of formation was calculated.
.
Temperature Correlated Properties
Properties
(Quality Code)
Vapor Pressure
I.G. Heat Capacity
(1)
(1)
Heat of Vaporization
Liquid Density
(0)
(0)
Liquid Heat Capacity
(3)
Methodology
Used the value of glucose.
Used a constant value for solid glucose at 20°C from the
literature 6 and assumed it was the same as the liquid heat
capacity. Using the heat of vaporization listed below, a single
parameter in this equation was adjusted to match the liquid heat
capacity.
Assumed an arbitrary low value of 1 kcal/mole at 298 K.
Assuming a value of water (1 g/cc) the Rackett parameter was
back calculated using the above critical properties and molecular
weight.
Used value for glucose on a mass basis.
Gypsum
Gypsum is considered to be a solid throughout the process and will never be in solution.
Point Properties
Properties
(Quality Code)
Molecular Weight
Solid Heat of Formation
(7)
(9)
Methodology
Calculated directly.
Literature value14.
16
@ 298.15 K
Solid Free Energy of
Formation @ 298.15 K
(9)
Literature value14.
Temperature Correlated Properties
Properties
Solid Heat Capacity
Solid Density
(Quality Code)
(2)
(9)
Methodology
Used literature value for CaSO414.
Literature value14.
17
References
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
Joback, Kevin G., “A Unified Approach to Physical Property Estimation Using Multivariate
Stastical Techniques”, MS Thesis, MIT, June 1982.
Pitzer, K. S., D. Z. Lippman, R. F. Curl, C. M. Huggins and D. E. Peterson, “The Volumetric and
Thermodynamic Properties of Fluids. II. Compressibility Factor, Vapor Pressure and Entropy of
Vaporization”, J. Am Chem. Soc., 77: 3433 (1955).
Zwolinski, B. J., Wilhoit, R., “Heats of Formation and Heats of Combustion” in “American Institute
of Physics Handbook”, 3rd ed., ed. by D. E. Gray pp. 4-316-342, McGraw-Hill, NY (1972).
Dean, John A., ed., “Lange’s Handbook of Chemistry”, 11th ed., McGraw-Hill, New York (1973), p.
9-98.
Benson, S. W., F. R. Cruickshank, D. M. Golden, G. R. Haugen, H. E. O’Neal, A. S. Rodgers, R. Shaw
and R. Walsh, “Additivity Rules for the Estimation of Thermochemical Properties”, Chem. Rev.,
69(3): 279 (1969).
Weast, Robert C., ed., “Handbook of Chemistry and Physics”, 53rd ed., CRC Press, Cleveland
(1973), p. D-192.
Watson, K. M., “Thermodynamics of the Liquid State, Generalized Prediction of Properties”, Ind.
Eng. Chem., 35: 398 (1943).
Rackett, H. G., “Equation of State for Saturated Liquids”, J. Chem. Eng. Data, 15(4): 514 (1970).
Dean, John A., ed., “Lange’s Handbook of Chemistry”, 11th ed., McGraw-Hill, New York (1973), p.
9-106.
Domalski, E. S., T. L. Jobe, Jr., T. A. Milne, “Thermodynamic Data for Biomass Materials and Waste
Components”, The American Society of Mechanical Engineers, New York (1987), p. 68.
Perry, Robert H., Cecil H. Chilton, eds., “Chemical Engineers’ Handbook”, 5th ed., McGraw-Hill,
New York (1973), p. 3-42.
Dean, John A., ed., “Lange’s Handbook of Chemistry”, 11th ed., McGraw-Hill, New York (1973), p.
9-126.
Dean, John A., ed., “Lange’s Handbook of Chemistry”, 11th ed., McGraw-Hill, New York (1973), p.
9-119.
Domalski, E. S., T. L. Jobe, Jr., T. A. Milne, “Thermodynamic Data for Biomass Materials and Waste
Components”, The American Society of Mechanical Engineers, New York (1987), p. 72.
C. Riley personal communication (1995).
Bailey, James E., David F. Ollis, “Biochemical Engineering Fundamentals”, 2nd ed., McGraw-Hill,
New York (1986) p. 294.
Robie, Richard A., Bruce S. Hemingway, James R. Fisher, “Thermodynamic Properties of Minerals
and Related Substances at 298.15 K and 1 Bar Pressure and at Higher Temperatures”, U.S.
Geological Survey Bulliten 1452, United States Government Printing Office, Washington (1979), p.
25.
Robie, Richard A., Bruce S. Hemingway, James R. Fisher, “Thermodynamic Properties of Minerals
and Related Substances at 298.15 K and 1 Bar Pressure and at Higher Temperatures”, U.S.
Geological Survey Bulliten 1452, United States Government Printing Office, Washington (1979), p.
320.
18
APPENDIX A
ASPEN Plus DFMS (Data File Management System) Input File
TITLE 'BIOFUELS DATABASE'
;
; Source Codes for Data
; 9 - Literature Data
; 8 - Regressed to Literature Data
; 7 - Calculated Directly (e.g. MW)
; 6 - Calculated from other Literature Data (e.g. delHf from delHc)
; 5 - Estimated using PREDICT (C)
; 4 - Estimated, but not from PREDICT (C)
; 3 - Used Literature Data for a Similar Compound on Mass Basis
; 2 - Used Literature Data for a Similar Compound on Molar Basis
; 1 - Copied from a "Similar" Compound
; 0 - Unknown Origin
;/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/
;
FILE
INHSPCD INHSPCD NEW
WRFILE INHSPCD
NEW-COMP GLUCOSE
C6H12O6
/
XYLOSE
C5H10O5
/
CELLULOS C6H10O5
/
XYLAN
C5H8O4
/
LIGNIN
CXHXOX
/
ZYMO
CHXOXNX
/
BIOMASS
CHXNXOXSX-1
/
CELLULAS CHXNXOXSX-2
/
SOLSLDS
CHXOXSX
/
SOLUNKN
CXHOX
/
GYPSUM
CASO4-2H2O
NEW-PROP
MW
1 /
TC
1 /
PC
1 /
VC
1 /
TB
1 /
OMEGA
1 /
DHFORM 1 /
DGFORM 1 /
DGSFRM 1 /
DHSFRM 1 /
PLXANT 9 /
DHVLWT 5 /
RKTZRA 1 /
CPIG
11 /
CPSPO1 8 /
VSPOLY 7 /
CPLDIP 7 /
THRSWT 8
;/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\
; Glucose
;
PROP-DATA
PROP-LIST
MW
7 /
TC
5 /
PC
5 /
VC
5 /
TB
5 /
OMEGA 5 /
DHFORM 6 /
DGFORM 9 /
RKTZRA 8
PVAL GLUCOSE
180.16
/
1011.1
/
0.62000E+07 /
0.41650
/
825.40
/
2.5674
/
-1.256903E+9 / -0.90933E+09 /
0.35852
;
PROP-LIST
CPIG
5
PVAL GLUCOSE
-5846.2
1005.4
-0.85893
0.28702E-03
-0.56533E-09
0.00000
573.15
1033.2
0.00000
0.00000
0.00000
19
;
PROP-LIST
PVAL GLUCOSE
PLXANT
1182.2
0.15640
2.0000
5
PROP-LIST
PVAL GLUCOSE
DHVLWT
5.02E+05
0.00000
0
-84682.
-175.85
573.15
0.00000
-0.23777E-04
993.15
;
298
200
0.38
;
PROP-LIST
PVAL GLUCOSE
CPLDIP 9
2.07431E5
0.00000
0.00000
0.0000
0.00000
250
1000
; THRSWT Element 6 required to invoke CPLDIP
PROP-LIST
THRSWT 0
PVAL GLUCOSE
1E35 1E35 1E35 1E35 1E35 1
;
; End of Glucose Data
;
;/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/
; Xylose
;
PROP-LIST
MW
7 /
TC
5 /
PC
5 /
VC
5 /
TB
5 /
OMEGA 5 /
DHFORM 6 /
RKTZRA 3
;
PVAL XYLOSE
150.132
/
890.42
/
0.65777E+07 /
0.34250
/
715.01
/
2.3042
/
-1.040002E+09 /
0.29936
;
PROP-LIST
PLXANT 5
PVAL XYLOSE
481.33
-46623.
0.00000
0.21007E-01
-64.331
0.62243E-05
2.0000
573.15
873.15
;
PROP-LIST
DHVLWT 0
PVAL XYLOSE
4.1868E6
298
0.38
0.00000
200
;
PROP-LIST
CPIG
5
PVAL XYLOSE
-4349.1
832.38
-0.70717
0.23520E-03
-0.20252E-09
0.00000
573.15
1023.2
0.00000
0.00000
0.00000
;
PROP-LIST
CPLDIP 3
PVAL XYLOSE
1.72857E5
0.00000
0.00000
0.0000
0.00000
250
1000
; THRSWT Element 6 required to invoke CPLDIP
PROP-LIST
THRSWT 0
PVAL XYLOSE
1E35 1E35 1E35 1E35 1E35 1
;
20
; End of Xylose Data
;
;/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\
; Cellulose
; (Considered a Solid)
;
PROP-LIST
MW 7
/
DHSFRM 6
PVAL CELLULOS 162.1436
/
-9.76362E8
;
PROP-LIST CPSPO1 9
PVAL CELLULOS -0.11704E5
.67207E3
0.00000
0.0000
0.00000
0.00000
298.15
1000
;
PROP-LIST VSPOLY 3
PVAL CELLULOS
0.10600
0.00000
0.00000
0.00000
0.00000
298.15
1000
;
; End of Cellulose Data
;
;\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\
; Xylan
; (Considered a Solid)
;
PROP-LIST
MW 7
/
DHSFRM 2
PVAL XYLAN
132.117
/
-7.62416E8
;
PROP-LIST CPSPO1 3
PVAL XYLAN
-0.95363E4
.54762E3
0.00000
0.0000
0.00000
0.00000
298.15
1000
;
PROP-LIST VSPOLY 3
PVAL XYLAN
0.08640
0.00000
0.00000
0.00000
0.00000
298.15
1000
;
; End of Xylan
;
;/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\
; Lignin
; (Considered a Solid)
; Formula of Lignin C7.3H13.9O1.3
;
PROP-LIST
MW 7
/
DHSFRM 6
PVAL LIGNIN 122.493
/
-1.592659E9
;
PROP-LIST CPSPO1 9
PVAL LIGNIN
3.14317E4
3.94427E2
0.00000
0.0000
0.00000
0.00000
298.15
1000
;
PROP-LIST VSPOLY 3
21
PVAL
LIGNIN
0.0817
0.00000
1000
0.00000
0.00000
0.00000
298.15
;
; End of Lignin Data
;
;/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\
; Cellulase (Enzyme)
; (Considered a Solid)
; Formula of Cellulase CH1.57N0.29O0.31S0.007
;
PROP-LIST
MW 7
/
DHSFRM 6
PVAL CELLULAS 22.8398 /
-7.4944E7
;
PROP-LIST CPSPO1 4
PVAL CELLULAS
3.5533E4
0.00000
0.00000
0.0000
0.00000
0.00000
298.15
1000
;
PROP-LIST VSPOLY 3
PVAL CELLULAS
0.0152
0.00000
0.00000
0.00000
0.00000
298.15
1000
;
; End of Cellulase Data
;
;\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/
; Biomass - Cell Mass
; (Considered a Solid)
; Formula of Biomass C H1.64 N0.23 O0.39 S0.0035
;
PROP-LIST
MW 7
/
DHSFRM 6
PVAL BIOMASS
23.238
/
-9.71338E7
;
PROP-LIST CPSPO1 4
PVAL BIOMASS
3.5910E4
0.00000
0.00000
0.0000
0.00000
0.00000
298.15
1000
;
PROP-LIST VSPOLY 3
PVAL BIOMASS
0.01549
0.00000
0.00000
0.00000
0.00000
298.15
1000
;
; End of Biomass Data
;
;\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/
; Zymo - Enzyme
; (Considered a Solid)
; Formula of Zymo C H1.8 O0.5 N0.2
;
PROP-LIST
MW 7
/
DHSFRM 4
PVAL ZYMO
24.6264
/
-1.305E8
;
22
PROP-LIST CPSPO1
PVAL ZYMO
4
PROP-LIST VSPOLY
PVAL ZYMO
3
3.8409E4
0.0000
298.15
0.00000
0.00000
1000
0.00000
0.00000
0.0164
0.00000
1000
0.00000
0.00000
0.00000
298.15
;
;
; End of Zymo Data
;
;/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/
; SOLSLDS
; (Considered a Mixed Component - Dissolved Solid)
;
Actual Formula: C H1.48 O.19 S.0013
;
PROP-LIST
MW
7 /
TC
1 /
PC
1 /
VC
1 /
TB
1 /
OMEGA 1 /
DHFORM 4 /
RKTZRA 0
;
PVAL SOLSLDS
16.5844
/
1011.1
/
0.62000E+07 /
0.41650
/
825.40
/
2.5674
/
-4.754E7
/
0.09908
;
PROP-LIST
CPIG
1
PVAL SOLSLDS
-5846.2
1005.4
-0.85893
0.28702E-03
-0.56533E-09
0.00000
573.15
1033.2
0.00000
0.00000
0.00000
;
PROP-LIST
PLXANT 1
PVAL SOLSLDS
1182.2
-84682.
0.00000
0.15640
-175.85
-0.23777E-04
2.0000
573.15
993.15
;
PROP-LIST
DHVLWT 0
PVAL SOLSLDS
4.1868E6
298
0.38
0.00000
200
;
PROP-LIST
CPLDIP 1
PVAL SOLSLDS
1.90948E4
0.00000
0.00000
0.0000
0.00000
250
1000
; THRSWT Element 6 required to invoke CPLDIP
PROP-LIST
THRSWT 0
PVAL SOLSLDS
1E35 1E35 1E35 1E35 1E35 1
;
; End of SOLSLDS Data
;
;/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/
; SOLUNKN (formerly Unknown)
; (Considered a Mixed Component - Dissolved Solid)
;
Actual Formula: C H1.48 O.19 S.0013
23
;
PROP-LIST
MW
VC
DHFORM
7
1
4
/
/
/
TC
TB
RKTZRA
1
1
0
/
/
PC
OMEGA
1
1
/
/
/
/
0.62000E+07
2.5674
/
/
;
PVAL
SOLUNKN
15.0134
0.41650
-1.19E8
/
/
/
1011.1
825.40
0.09404
;
PROP-LIST
PVAL SOLUNKN
CPIG
1
-5846.2
0.28702E-03
573.15
0.00000
PROP-LIST
PVAL SOLUNKN
PLXANT
1182.2
0.15640
2.0000
1
PROP-LIST
PVAL SOLUNKN
DHVLWT
4.1868E6
0.00000
0
1005.4
-0.56533E-09
1033.2
0.00000
-0.85893
0.00000
0.00000
;
-84682.
-175.85
573.15
0.00000
-0.23777E-04
993.15
;
298
200
0.38
;
PROP-LIST
PVAL SOLUNKN
CPLDIP 1
1.72860E4
0.00000
0.00000
0.0000
0.00000
250
1000
; THRSWT Element 6 required to envoke CPLDIP
PROP-LIST
THRSWT 0
PVAL SOLUNKN
1E35 1E35 1E35 1E35 1E35 1
;
; End of SOLUNKN Data
;
;
;\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/
; Gypsum
;
Solid
; Formula of Gypsum CaSO4-2H2O
;
PROP-LIST
MW 7
/
DHSFRM 9
/ DGSFRM 9
PVAL GYPSUM
172.168
/
-2.022628E9 / -1.797197E9
;
PROP-LIST CPSPO1 2
PVAL GYPSUM
7.2182E4
9.73430E1
0.00000
0.0000
-1.3733E8
0.00000
298
1400
;
PROP-LIST VSPOLY 9
PVAL GYPSUM
0.07469
0.00000
0.00000
0.00000
0.00000
298.15
1000
;
; End of Gypsum Data
24
;
PRINT-DIR INHSPCD ALL
PRINT-DATA INHSPCD ALL
END-INPUT
25
APPENDIX B
ASPEN Plus PROP-DATA Input File
PROP-REPLACE NRTL NRTL
PROP DHL DHL09
COMPONENTS
NEW-COMP GLUCOSE
/
XYLOSE
/
CELLULOS /
XYLAN
/
LIGNIN
/
ZYMO
/
BIOMASS
/
CELLULAS /
SOLSLDS
/
SOLUNKN
/
GYPSUM
;/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\
; Glucose
;
PROP-DATA
PROP-LIST
MW
/
TC
/
PC
/
VC
/
TB
/
OMEGA
/
DHFORM
/
DGFORM
/
RKTZRA
PVAL GLUCOSE
180.16
/
1011.1
/
0.62000E+07 /
0.41650
/
825.40
/
2.5674
/
-1.256903E+9 / -0.90933E+09 /
0.35852
;
PROP-LIST
CPIG
PVAL GLUCOSE
-5846.2
1005.4
-0.85893
&
0.28702E-03
-0.56533E-09
0.00000
&
573.15
1033.2
0.00000
&
0.00000
0.00000
;
PROP-LIST
PLXANT
PVAL GLUCOSE
1182.2
-84682.
0.00000
&
0.15640
-175.85
-0.23777E-04 &
2.0000
573.15
993.15
;
PROP-LIST
DHVLWT
PVAL GLUCOSE
5.02E+05
298
0.38
&
0.00000
200
;
PROP-LIST
CPLDIP
PVAL GLUCOSE
2.07431E5
0.00000
0.00000
&
0.0000
0.00000
250
&
1000
;
; End of Glucose Data
;
;/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/
; Xylose
26
;
PROP-LIST
MW
VC
DHFORM
/
/
/
TC
TB
RKTZRA
/
/
PC
OMEGA
/
/
;
PVAL
XYLOSE
150.132
/
0.34250
/
-1.040002E+09 /
890.42
715.01
0.29936
/
/
0.65777E+07 /
2.3042
/
;
PROP-LIST
PVAL XYLOSE
PLXANT
481.33
0.21007E-01
2.0000
PROP-LIST
PVAL XYLOSE
DHVLWT
4.1868E6
0.00000
PROP-LIST
PVAL XYLOSE
CPIG
-4349.1
0.23520E-03
573.15
0.00000
PROP-LIST
PVAL XYLOSE
CPLDIP
1.72857E5
0.0000
1000
-46623.
-64.331
573.15
0.00000
0.62243E-05
873.15
&
&
0.38
&
;
298
200
;
832.38
-0.20252E-09
1023.2
0.00000
-0.70717
0.00000
0.00000
&
&
&
0.00000
250
&
&
;
0.00000
0.00000
;
; End of Xylose Data
;
;/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\
; Cellulose
; (Considered a Solid)
;
PROP-LIST
MW
/
DHSFRM
PVAL CELLULOS 162.1436
/
-9.76362E8
;
PROP-LIST CPSPO1
PVAL CELLULOS -0.11704E5
.67207E3
0.00000
&
0.0000
0.00000
0.00000
&
298.15
1000
;
PROP-LIST VSPOLY
PVAL CELLULOS
0.10600
0.00000
0.00000
&
0.00000
0.00000
298.15
&
1000
;
; End of Cellulose Data
;
;\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\
; Xylan
; (Considered a Solid)
;
27
PROP-LIST
PVAL XYLAN
MW
132.117
/
/
DHSFRM
-7.62416E8
;
PROP-LIST CPSPO1
PVAL XYLAN
-0.95363E4
0.0000
298.15
.54762E3
0.00000
1000
0.00000
0.00000
&
&
0.00000
0.00000
0.00000
298.15
&
&
;
PROP-LIST VSPOLY
PVAL XYLAN
0.08640
0.00000
1000
;
; End of Xylan
;
;/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\
; Lignin
; (Considered a Solid)
; Formula of Lignin C7.3H13.9O1.3
;
PROP-LIST
MW
/
DHSFRM
PVAL LIGNIN 122.493
/
-1.592659E9
;
PROP-LIST CPSPO1
PVAL LIGNIN
3.14317E4
3.94427E2
0.00000
&
0.0000
0.00000
0.00000
&
298.15
1000
;
PROP-LIST VSPOLY
PVAL LIGNIN
0.0817
0.00000
0.00000
&
0.00000
0.00000
298.15
&
1000
;
; End of Lignin Data
;
;/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\
; Cellulase (Enzyme)
; (Considered a Solid)
; Formula of Cellulase CH1.57N0.29O0.31S0.007
;
PROP-LIST
MW
/
DHSFRM
PVAL CELLULAS 22.8398 /
-7.4944E7
;
PROP-LIST CPSPO1
PVAL CELLULAS
3.5533E4
0.00000
0.00000
&
0.0000
0.00000
0.00000
&
298.15
1000
;
PROP-LIST VSPOLY
PVAL CELLULAS
0.0152
0.00000
0.00000
&
0.00000
0.00000
298.15
&
1000
;
; End of Cellulase Data
28
;
;\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/
; Biomass - Cell Mass
; (Considered a Solid)
; Formula of Biomass C H1.64 N0.23 O0.39 S0.0035
;
PROP-LIST
MW
/
DHSFRM
PVAL BIOMASS
23.238
/
-9.71338E7
;
PROP-LIST CPSPO1
PVAL BIOMASS
3.5910E4
0.00000
0.00000
&
0.0000
0.00000
0.00000
&
298.15
1000
;
PROP-LIST VSPOLY
PVAL BIOMASS
0.01549
0.00000
0.00000
&
0.00000
0.00000
298.15
&
1000
;
; End of Biomass Data
;
;\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/
; Zymo - Enzyme
; (Considered a Solid)
; Formula of Zymo C H1.8 O0.5 N0.2
;
PROP-LIST
MW
/
DHSFRM
PVAL ZYMO
24.6264
/
-1.305E8
;
PROP-LIST CPSPO1
PVAL ZYMO
3.8409E4
0.00000
0.00000
&
0.0000
0.00000
0.00000
&
298.15
1000
;
PROP-LIST VSPOLY
PVAL ZYMO
0.0164
0.00000
0.00000
&
0.00000
0.00000
298.15
&
1000
;
; End of Zymo Data
;
;/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/
; SOLSLDS
; (Considered a Mixed Component - Dissolved Solid)
;
Actual Formula: C H1.48 O.19 S.0013
;
PROP-LIST
MW
/
TC
/
PC
/
VC
/
TB
/
OMEGA
/
DHFORM
/
RKTZRA
;
PVAL SOLSLDS
16.5844
/
1011.1
/
0.62000E+07 /
0.41650
/
825.40
/
2.5674
/
-4.754E7
/
0.09908
;
29
PROP-LIST
PVAL SOLSLDS
CPIG
-5846.2
0.28702E-03
573.15
0.00000
PROP-LIST
PVAL SOLSLDS
PLXANT
1182.2
0.15640
2.0000
PROP-LIST
PVAL SOLSLDS
DHVLWT
4.1868E6
0.00000
PROP-LIST
PVAL SOLSLDS
CPLDIP
1.90948E4
0.0000
1000
1005.4
-0.56533E-09
1033.2
0.00000
-0.85893
0.00000
0.00000
&
&
&
0.00000
-0.23777E-04
993.15
&
&
;
-84682.
-175.85
573.15
;
298
200
0.38
&
0.00000
250
&
&
;
0.00000
0.00000
;
; End of SOLSLDS Data
;
;/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/
; SOLUNKN (formerly Unknown)
; (Considered a Mixed Component - Dissolved Solid)
;
Actual Formula: C H1.48 O.19 S.0013
;
PROP-LIST
MW
/
TC
/
PC
/
VC
/
TB
/
OMEGA
/
DHFORM
/
RKTZRA
;
PVAL SOLUNKN
15.0134
/
1011.1
/
0.62000E+07 /
0.41650
/
825.40
/
2.5674
/
-1.19E8
/
0.09404
;
PROP-LIST
CPIG
PVAL SOLUNKN
-5846.2
1005.4
-0.85893
&
0.28702E-03
-0.56533E-09
0.00000
&
573.15
1033.2
0.00000
&
0.00000
0.00000
;
PROP-LIST
PLXANT
PVAL SOLUNKN
1182.2
-84682.
0.00000
&
0.15640
-175.85
-0.23777E-04 &
2.0000
573.15
993.15
;
PROP-LIST
DHVLWT
PVAL SOLUNKN
4.1868E6
298
0.38
&
0.00000
200
;
PROP-LIST
CPLDIP
PVAL SOLUNKN
1.72860E4
0.00000
0.00000
&
0.0000
0.00000
250
&
1000
30
;
; End of SOLUNKN Data
;
;\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/\/
; Gypsum
;
Solid
; Formula of Gypsum CaSO4-2H2O
;
PROP-LIST
MW
/
DHSFRM
/ DGSFRM
/
PVAL GYPSUM
172.168
/
-2.022628E9 / -1.797197E9
;
PROP-LIST CPSPO1
PVAL GYPSUM
7.2182E4
9.73430E1
0.00000
&
0.0000
-1.3733E8
0.00000
&
298
1400
;
PROP-LIST VSPOLY
PVAL GYPSUM
0.07469
0.00000
0.00000
&
0.00000
0.00000
298.15
&
1000
;
; End of Gypsum Data
;
31
APPENDIX C
Quality of Properties in INHSPCD Databank for ASPEN Plus
Single Point Values
Temperature Correlations
Compound Primary Database
Phase Alias
MW
TC
PC
VC
Glucose
VL
C6H12O6
7
5
5
5
Xylose
VL
C5H10O5
7
5
5
5
Cellulose S
C6H10O5
7
Xylan
S
C5H8O4
7
Lignin
S
CXHXOX
7
Zymo
S
CHXOXNX
7
Cellulas
S
CHXNXOXSX-2
7
Biomass
S
CHXNXOXSX-1
7
Solunkn
VL
CXHOX
7
1
1
1
SolSlds
VL
CHXOXSX
7
1
1
1
Gypsum
S
CASO4-2H2O
7
*Solid Properties
Source Codes for Data
9 - Literature Data
8 - Regressed to Literature Data
7 - Calculated Directly (e.g. MW)
6 - Calculated from other Literature Data (e.g. delHf from delHc)
5 - Estimated using PREDICT (C)
4 - Estimated, but not from PREDICT (C)
3 - Used Literature Data for a Similar Compound on Mass Basis
2 - Used Literature Data for a Similar Compound on Molar Basis
1 - Copied from a "Similar" Compound
0 - Unknown Origin
OMEGA DHFORM DGFORM DHSFRM*
5
5
6
6
9
RKTZRA
PLXANT DHVLWT
CPIG
8
3
5
5
0
0
5
5
0
0
1
1
0
0
1
1
6
2
6
4
6
6
1
1
4
4
9
33
CPLDIP CPSPO1* VSPOLY
*
9
3
9
3
3
3
9
3
4
3
4
3
4
3
3
3
2
9
Appendix D
Values in ASPEN Plus INHSPCD (NREL Biofuels) Databank
Property
Molecular Weight
Critical Temperature
Critical Pressure
Critical Volume
Acentric Factor
I.G. Heat of Formation
I.G. Free Energy of Form.
Solid Heat of Formation
Solid Free Energy of Form.
Vapor Pressure
Heat of Vaporization
Liquid Molar Volume
Solid Molar Volume
I.G. Heat Capacity
Solid Heat Capacity
Liquid Heat Capacity
Aspen
Property
MW
TC
PC
VC
OMEGA
DHFORM
DGFORM
DHSFRM
DGSFRM
PLXANT/1
PLXANT/2
PLXANT/3
PLXANT/4
PLXANT/5
PLXANT/6
PLXANT/7
PLXANT/8
PLXANT/9
DHVLWT/1
DHVLWT/2
DHVLWT/3
DHVLWT/4
DHVLWT/5
RKTZRA
VSPOLY/1
VSPOLY/2
VSPOLY/3
VSPOLY/4
VSPOLY/5
VSPOLY/6
VSPOLY/7
CPIG/1
CPIG/2
CPIG/3
CPIG/4
CPIG/5
CPIG/6
CPIG/7
CPIG/8
CPIG/9
CPIG/10
CPIG/11
CPSPO1/1
CPSPO1/2
CPSPO1/3
CPSPO1/4
CPSPO1/5
CPSPO1/6
CPSPO1/7
CPSPO1/8
CPLDIP/1
CPLDIP/2
CPLDIP/3
CPLDIP/4
CPLDIP/5
CPLDIP/6
CPLDIP/7
Units
K
Pascal
cum/Kmole
J/Kmole
J/Kmole
J/Kmole
J/Kmole
Pascal
J/Kmole
cum/Kmole
cum/Kmole
J/Kmole K
Glucose
180.16
1011.1
6,200,000
0.4165
2.5674
-1,256,903,000
-909,330,000
Xylose
150.132
890.42
6,577,700
0.3425
2.3042
-1,040,020,000
1182.2
-84682
0
0.1564
-175.85
-2.37770E-05
2
573.15
993.15
502,000
298
0.38
0
200
0.35852
481.33
-46623
0
2.10E-02
64.331
6.22430E-06
2
573.15
873.15
4,186,800
298
0.38
0
200
0.29936
Xylan
132.117
Lignin
122.493
Cellulase
22.8398
Zymo
24.6264
Biomass
23.238
-976,362,000
-762,416,000
-1,592,659,000
-74,944,000
-130,500,000
-97,133,800
0.106
0
0
0
0
298.15
1000
-5846.2
1005.4
-0.85893
2.87020E-04
-5.65330E-10
0
573.15
1033.2
0
0
0
0.0817
0
0
0
0
298.15
1000
0.0152
0
0
0
0
298.15
1000
0.0164
0
0
0
0
298.15
1000
Solslds
16.5844
1011.1
6,200,000
0.4165
2.5674
-47,540,000
Solunkn
15.0134
1011.1
6,200,000
0.4165
2.5674
-119,000,000
1182.2
-84682
0
0.1564
-175.85
-2.37770E-05
2
573.15
993.15
4,186,800
298
0.38
0
200
0.09908
1182.2
-84682
0
0.1564
-175.85
-2.37770E-05
2
573.15
993.15
4,186,800
298
0.38
0
200
0.09404
-9529.9
547.25
0
0
0
0
298.15
1000
172857
0
0
0
0
250
1000
31431.7
394.427
0
0
0
0
298.15
1000
35533
0
0
0
0
0
298.15
1000
38409
0
0
0
0
0
298.15
1000
0.01549
0
0
0
0
298.15
1000
0.07469
0
0
0
0
298.15
1000
-5846.2
1005.4
-0.85893
2.87020E-04
-5.65330E-10
0
573.15
1033.2
0
0
0
35910
0
0
0
0
0
298.15
1000
72,182
97.343
0
0
-137,330,000
0.00E+00
298
1400
19094
0
0
0
0
250
1000
34
Gypsum
172.168
-2,022,628,000
-1,797,197,000
-5846.2
1005.4
-0.85893
2.87020E-04
-5.65330E-10
0
573.15
1033.2
0
0
0
-11704
672.07
0
0
0
0
298.15
1000
207431
0
0
0
0
250
1000
0.0864
0
0
0
0
298.15
1000
-4349.1
832.38
-0.70717
2.35200E-04
-2.02520E-10
0
573.15
1023.2
0
0
0
J/Kmole K
J/Kmole K
Cellulose
162.1436
17286
0
0
0
0
250
1000
APPENDIX E
Data Values in ASPEN Plus NREL Biofuels INHSPCD Databank
Temperature Correlations Used in ASPEN Plus
Vapor Pressure - PLXANT
C 2i
*,l
ln p i = C 1i +
T + C 3i
+ C 4i T + C 5i ln T + C 6 i T
C 7i
for
C 8i ≤ T ≤ C 9i
Where,
PLXANT/1....9 correspond to C1i....9i
Watson Heat of Vaporization - DHVLWT
∆
*
vapH i ( T ) =
∆
 1 − T / T a i + bi (1− T / T ci )
ci

for
 1 − T1 / Tci 
*

vapH i ( T1 ) 
Where,
*
∆ vapH i ( T1 ) = Heat of Vaporization at temperature T1
Parameter
TC
DHVLWT/1
Symbol
Tci
*
∆ vapH i ( T1 )
DHVLWT/2
DHVLWT/3
DHVLWT/4
DHVLWT/5
T1
ai
bi
Tmin
Rackett Liquid Molar Volume - RKTZRA
35
T > Tmin
RA [1+(1− Tr )
l
Vm
=
2/ 7
RTc ( Z m )
]
pc
Where,
Tc =
∑ ∑x x V
i
i
Tc
pc
=
2
k ij ) / Vcm
Tci
i
i
RA
1/ 2
(1 −
ci Vcj ( Tci Tcj )
j
∑x
Zm =
j
p ci
∑x Z
i
*,RA
i
i
Vcm =
∑x V
i
ci
i
Tr =
T
Tc
Parameter
TC
PC
VC
RKTZRA
RKTKIJ
Symbol
Tci
pci
Vci
RA
Zi
k ij
Solids Volume Polynomial - VSPOLY
Vi
*,s
2
3
( T ) = C 1i + C 2i T + C 3i T + C 4 i T + C 5i T
4
for
C 6 i ≤ T ≤ C 7i
Where,
VSPOLY/1....7 correspond to C1i....7i
Ideal Gas Heat Capacity - CPIG
*,ig
2
3
4
C p ( T ) = C 1i + C 2i T + C 3i T + C 4 i T + C 5 i T + C 6i T
*,ig
C p ( T) =
C 9i + C 10 i T
5
for
C 7 i ≤ T ≤ C 8i
T < C7 i
for
Where,
CPIG/1....11
correspond to C1i....11i
Solids Heat Capacity
*,s
2
C p,i ( T ) = C 1i + C 2i T + C 3i T +
C 4i
T
+
C 5i
T
2
+
C 6i
T
for
Where,
CPSP01/1....8 correspond to C1i....8i
36
C7 i ≤ T ≤ C 8 i
DIPPR Liquid Heat Capacity - CPLDIP
*,l
2
3
C p,i ( T ) = C 1i + C 2i T + C 3i T + C 4 i T + C 5 i T
4
for
Where,
CPLDIP/1....7
correspond to C1i....7i
37
C 6 i ≤ T ≤ C 7i
APPENDIX F
ASPEN PLUS Physical Property Route Modifications to Enable the
DIPPR Liquid Heat Capacity Correlation
The standard physical property calculation route in ASPEN PLUS does not use a correlation for liquid heat
capacity; rather, it uses correlations for the ideal gas heat capacity and the heat of vaporization. For some
compounds studied here, which exist in the liquid phase, a liquid heat capacity rather than a heat of
vaporization or gas heat capacity was available. To take advantage of these data, the DIPPR correlation for
liquid heat capacity (available in ASPEN PLUS) was used. To enable this model, a modification to the
physical property route was necessary. This modification is:
PROP-REPLACE NRTL NRTL
PROP DHL DHL09
These imput language statements (also available in Model Manager) modify the basic physical property
option set, NRTL, to use the DIPPR liquid heat capacity route, DHL09, for the calculation of liquid
enthalphy, DHL09.
With this modification, the DIPPR liquid heat capacity model will be used only if data are present. If no data
are present for this model (CPLDIP), the calculations will revert to the standard methods of using the IG heat
capacity and heat of vaporization.
This method has a bug in it that Aspen Technology is not willing to fix at this time. Therefore, even though
this was a good method for calculating the necessary liquid heat capacity, it was not available as of this
writing.
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